Catalytic cracking is a petroleum refining process which is applied commercially on a very large scale. A majority of the refinery gasoline blending pool in the United States is produced by this process, with almost all being produced using the fluid catalytic cracking (FCC) process. In the catalytic cracking process heavy hydrocarbon fractions are converted into lighter products by reactions taking place at elevated temperature in the presence of a catalyst, with the majority of the conversion or cracking occurring in the vapor phase. The feedstock is thereby converted into gasoline, distillate and other liquid cracking products as well as lighter gaseous cracking products of four or less carbon atoms per molecule. The gas partly consists of olefins and partly of saturated hydrocarbons.
During the cracking reactions some heavy material, known as coke, is deposited onto the catalyst. This reduces the activity of the catalyst and regeneration is desired. After removal of occluded hydrocarbons from the spent cracking catalyst, regeneration is accomplished by burning off the coke to restore catalyst activity. The three characteristic steps of the catalytic cracking can be therefore be distinguished: a cracking step in which the hydrocarbons are converted into lighter products, a stripping step to remove hydrocarbons adsorbed on the catalyst and a regeneration step to burn off coke from the catalyst. The regenerated catalyst is then reused in the cracking step.
Catalytic cracking feedstocks normally contain sulfur in the form of organic sulfur compounds such as mercaptans, sulfides and thiophenes. The products of the cracking process correspondingly tend to contain sulfur impurities even though about half of the sulfur is converted to hydrogen sulfide during the cracking process, mainly by catalytic decomposition of non-thiophenic sulfur compounds. The distribution of sulfur in the cracking products is dependent on a number of factors including feed, catalyst type, additives present, conversion and other operating conditions but, in any event a certain proportion of the sulfur tends to enter the light or heavy gasoline fractions and passes over into the product pool. With increasing environmental regulation being applied to petroleum products, for example in the Reformulated Gasoline (RFG) regulations, the sulfur content of the products has generally been decreased in response to concerns about the emissions of sulfur oxides and other sulfur compounds into the air following combustion processes.
One approach has been to remove the sulfur from the FCC feed by hydrotreating before cracking is initiated. While highly effective, this approach tends to be expensive in terms of the capital cost of the equipment as well as operationally since hydrogen consumption is high. Another approach has been to remove the sulfur from the cracked products by hydrotreating. Again, while effective, this solution has the drawback that valuable product octane may be lost when the high octane olefins are saturated.
From the economic point of view, it would be desirable to achieve sulfur removal in the cracking process itself since this would effectively desulfurize the major component of the gasoline blending pool without additional treatment. Various catalytic materials have been developed for the removal of sulfur during the FCC process cycle, but, so far most developments have centered on the removal of sulfur from the regenerator stack gases. An early approach developed by Chevron used alumina compounds as additives to the inventory of cracking catalyst to adsorb sulfur oxides in the FCC regenerator; the adsorbed sulfur compounds which entered the process in the feed were released as hydrogen sulfide during the cracking portion of the cycle and passed to the product recovery section of the unit where they were removed. See Krishna et al, Additives Improve FCC Process, Hydrocarbon Processing, November 1991, pages 59-66. The sulfur is removed from the stack gases from the regenerator but product sulfur levels are not greatly affected, if at all.
An alternative technology for the removal of sulfur oxides from regenerator stack gases is based on the use of magnesium-aluminum spinels as additives to the circulating catalyst inventory in the FCCU. Under the designation DESOX™ used for the additives in this process, the technology has achieved a notable commercial success. Exemplary patents disclosing these types of sulfur removal additives include U.S. Pat. Nos. 4,963,520; 4,957,892; 4,957,718; 4,790,982 and others. Again, however, product sulfur levels are not greatly reduced.
A catalyst additive for the reduction of sulfur levels in the liquid cracking products was proposed by Wormsbecher and Kim in U.S. Pat. Nos. 5,376,608 and 5,525,210, using a cracking catalyst additive of an alumina-supported Lewis acid for the production of reduced-sulfur gasoline.
U.S. Pat. No. 6,482,315 discloses a supported vanadium catalyst for sulfur reduction in the form of a separate particle additive. The support material may be organic or inorganic in nature and may be porous or non-porous. Preferably, the support material is an amorphous or paracrystalline inorganic oxide such as, for example, Al2O3, SiO2, clays or mixtures thereof. The sulfur reduction additives are used as separate particle additives in combination with the conventional catalytic cracking catalyst (normally a faujasite such as zeolite Y) to process hydrocarbon feedstocks in the fluid catalytic cracking (FCC) unit to produce low-sulfur gasoline and other liquid cracking products, such as, for example, light cycle oil that can be used as a low sulfur diesel blend component or as heating oil. The preferred support is alumina. The sulfur reduction additive has a high V content of from 2 to 20 wt. %.
Published patent application, US 2004/0099573 intentionally adds vanadium to the feed stream during operation of the FCC unit. The amount of vanadium compound added to the feed will vary depending upon such factors as the nature of the feedstock used, the cracking catalyst used and the results desired. Generally, the vanadium compound is added to the feed at a rate sufficient to increase the concentration of vanadium in or on the equilibrium catalyst inventory by about 100 to about 20,000 ppm, preferably about 300 to about 5000 ppm, most preferably about 500 to about 2000 ppm, relative to the amount of vanadium initially present in or on the catalyst inventory. The preferred vanadium compounds are selected from vanadium oxalate, vanadium sulfate, vanadium naphthenate, vanadium halides, and mixtures thereof.
U.S. Pat. No. 6,635,169 discloses that a metal component (i.e. V) located within the interior of a zeolite pore structure works much more effectively in gasoline sulfur reduction in its oxidized state. The improvement comprises increasing the average oxidation state of the metal component of the regenerated cracking catalyst by further oxidative treatment.
Three patents granted to Mobil and W. R. Grace jointly, (U.S. Pat. No. 6,846,403, U.S. Pat. No. 6,923,903 and U.S. Pat. No. 6,974,787) disclose a method of reducing gasoline sulfur using a metal-containing zeolite catalyst where a first metal (preferably vanadium) in an oxidation state above zero is located within the interior pore structure of the zeolite together with a second metal of a rare earth component (preferably cerium). The presence of both vanadium and rare earth metal on the catalyst gives rise to better gasoline sulfur reduction than vanadium alone, possibly due to the high active sites retention with rare earth metals.